Alkanethiols (CH3(CH2)n-1SH) based self-assembled monolayers (SAMs) on the clean copper surfaces have been examined for n = 4, 8, and 16. Using X-ray photoelectron spectroscopy (XPS) and contact angle analysis, it is found that alkanethiolate monolayers similar to those on gold are formed on clean copper surfaces. The monolayers are stable in air up to about 140 $^{circ}C.$ Above 160 $^{circ}C$ the monolayers begin to desorb through the oxidation reaction of the thiolate to sulfonate, with the alkyl chains remaining intact. Following this desorption step, the copper surface has begun to oxidize to CuO at about 180 $^{circ}C$.